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Proceedings of the Chemical Society, Vol. 18, No. 254 |
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Proceedings of the Chemical Society, London,
Volume 18,
Issue 254,
1902,
Page 159-178
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摘要:
Issued 25/6/02 PROCEEDINGS OF THE CHEMICAL SOCIETY. EDZTED BY THB SECRETARIES. Vol. 18. No. 254. Wednesday, June 18th, 1902. Professor ENERSON Sc.D.,REYNOLDS, V.P.R.S., President, in the Chair. Messrs. Russell, Lattey, Ionides, Haas, and Heaton mere formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. : Guy Dunstan Ricketts, Sir John Cass Technical Institute, E.C. Edgar Stansfield, B.Sc., Technical College, Sunderland. Thomas Edward Wallis, 78, Essex Road, Islington, N. The PRESIDENTannounced that the Council that afternoon had decided that the Ordinary Meetings of the Society for the ensuing session should be held, as far as possible, alternately, on Wednesdays at 5.30 p.m. and Thursdays at 8 p.m.160 A Ballot for the Election of Fellows was held, and the following were subsequently declared duly elected : James Handby Ball, B.Sc. Thomas Henry Moore. Edwin Thomas Holmsn Bucknell. Sinnott Valentine O’Connor. Bryce Chudleigh Burt, B.Sc. Percy Philip Phillips, Ph. D. Arthur Crozier Claudet. George Paton Pollitt, Ph.D. WilIiam Thomas Clough. William E. F. Powney.Henry Wilson Davis. Herbert Portan. Percy J. Ferris. Stephen Jamieson Ralph. Edgar William Foll. Edwin Ralphs. Francis E. Francis, B.Sc., Ph.D. Prafulla Chandra RBy, D.Sc. John Longsdon Garle. Harold James Roast. Alexander Gow, B.Sc. William Pearson Skertchly. Thomas B. Hallowell. William C. S. Stanger. Archie Cecil Osborn Hann. Hector Stewart.Walter Ernest Harrison. John William Wells. George Herbert Leader, B.Sc. Joseph West. Charles B. Lessner. Edward J. Wheeler. James Butler Moody. Of the following papers, those marked * were read : *106. Elimination of a nitro-group on diazotisation. Dinitro-p anisidine.” By 11. Meldola and J. V.Eyre. Dinitro-p-anisidine, obtained by nitrating ncet-p-anisidide and hydrolysing the acetyl derivative, was shown by the authors to have the constitution C6H2N02*N0,*NH,*OCHs=2 :3 :4: 1. This com-pound, on diazotisation in acetic acid in presence of sulphuric or nitric acid, behaves normally and forms a dinitrodiazonium salt, which on heating with alcohol gives dinitroanisole, C6H,-N02*N02*OCH,= 2 :3 : 1, of m. p. 119O. The dinitrodiazonium salts combine with alkaline &naphthol in the ordinary way to form the azo-compound, CH,0*C6H2(N0,)2-N2~C,,H6*OH~.When diazotised in the presence of hydrochloric or acetic acid, one of the nitro-groups is eliminated as in the case of dinitro-o-anisidine (F~uns.,1900,7’7, 1172 ; PYOC.,1901, 17,131 ; Tk7zs., 1901, 79, 1076).The authors showed that it is the 3-nitro-group, that is, the group which is ovtho with respect to the diazoniurn group, which is thus eliminated. The product, when hydro- chloric acid is used, contains chlorine in place of the 3-nitro-group, and is formed according to the scheme : 161 No diazoxide appears to be formed in this case, but the replacement of the nitro-group by chlorine takes place at once at the ordinary tem- perature.The chloronitrodiazonium salt, when boiled with alcohol, with or without the addition of alkali, gives chloronitroanisole, C,H,*Cl*NO,~OCH,=3 :2 :1. The same diazonium salt, on combina-tion with alkaline P-naphthol, gives the azo-compound, CH,O~C,H,Cl~NO,*N,*C,,H,=OH~.When diazotised in the presence of acetic acid alone, the NO, group is replaced by hydroxyl, and the diazonium salt combines with P-naphthol to form the hydroxyazo- compound, CH,O~C,H,-NO,*OH*N,*C,,H,~OH~.In this case, a N2diazoxide, CH,O~C,H,*NO,<C) ,may be formed as an intermediate product, but this has not yet been isolated. The displacing of the nitro-group in the two dinitroanisidines now investigated tends to show that the elimination of this group follows the ortho-para law, and experiments for the purpose of testing this con- clusion will be undertaken in due course.“107. Preliminary notice of some new derivatives of pinene and other terpenes.” By W. A. Tilden and H. Burrows. Pinene nitrosochloride is remarkable as being the only known com-pound containing the elements of pinene from which that hydrocarbon may be regenerated. The addition of one molecule of hydrogen chloride to pinene gives the familiar monohydrochloride (artificial camphor, m. p. l28O), from which, by withdrawal of hydrogenchloride, camphene, and not pinene, results. The addition of two molecules of hydrogen chloride to pinene gives rise to dipentene dihydrochloride (m. p. SO’), from which, by removal of 2 molecules of hydrogen chloride, a mixture of liquid isomerides of pinene is obtained.On the other hand, when pinene combines with nitrosylchloride, a compound is formed which contains a nitroso-group. This is indicated by the fact that it is capable of reacting with aniline to yield a diazotised product, leaving a hydrocarbon which is apparently identical with pinene, though optically inactive (Waliach, Ann., lSS9, 252,132 ; 1890, 258,344). The authors have repeated this experiment, andalthoughthereactionis not so simple as they were led to infer from Wallach’s account of it,they have verified the fact that the recovered hydrocarbon combines readily with nitrosylchloride, forming a nitrosochloride which melts at 1loo, and from which a benzylnitrolamine melting at 125’ was obtained.The corresponding compounds formed from ordinary dextro-pinene melt at 103’ and 122-123’ respectively (Wallach). The fact that this recovered pinene is optically inactive but not resolv-able into two optical isomerides has not attracted the attention it 162 deserves. If optically inactive pinene really possesses the same con- stitution as active pinene, this would imply the existence in the mole-cule of two asymmetric carbon atoms similarly combined. The formula given by Wallach, Wagner, and other chemists are therefore inadequate to explain the facts. In the hope of getting some new light on the problem, attempts have been made to produce new derivatives of the hydrocarbon by adding carbon in various forms to the unsaturated part of the molecule, with the idea of obtaining acids or other compounds of determinable constitution, Several methods have been tested in a preliminary way, but at present only one has met with success.When pinene nitrosochloride is gently heated with an equivalent quantity of potassium cyanide in the presence of 90 per cent. alcohol, a compound having the composition of pinene nitrosocyanide is formed amounting to about 40 per cent. of the nitrosochloride employed. The viscous bye-products have not been completely exam- ined. The cyanide is a crystalline compound which forms large prisms, of which the melting point is 171'. On analysis, the compound gave 14-47 per cent. of nitrogen, C,,H,,XOCN, requiring 14.58 per cent.It dissolves readily in alcohol, ether, acetic acid, and toluene, but very sparingly in light petroleum, and it is practically insoluble in water. The constitution of this nitrosocyanide is at present an unsettled question, It is unaltered by boiling with 30 per cent. alcoholicpotash for several hours. On the other hand, it is completely destroyed with formation of uncrystallisable products when heated with dilute sul- phuric acid or with hydrochloric acid, either in alcoholic solution or in glacial acetic acid at 100'. It is therefore doubtful whether the com-pound is a nitrile. There are, however, other cases on record of nitriles which resist the action of alkalis, and the question is still under invest- igation.By digesting the cyanide with alcoholic potash and methyl iodide, a methyl derivative is produced which is distinguished by the readiness with which it forms large, colourless, prismatic crystals. The melting point of this compound is 67', and it contains 13-64 per cent. of nitrogen, CIoH,,CH,*NO*CNrequiring 13.60 per cent. The action of reducing agents on the cyanide is rather remarkable. Three methods were successively employed, namely, (1) the action of sodium on a boiling solution of the cyanide in amyl elcohol, (2) the action of sodium on a boiling solutiou in ethyl alcohol, and (3) the action of zinc in the presence of alcohol and hydrochloric acid. In the reductions with sodium, some ammonia was evolved, and a cyanide was produced in considerable quantity, together with an almost quantita- tive yield of pinylamine.The acid reducing agent produced practically no change, but when 163 zinc dust and an alkaline solution were employed ammonia was evolved, and on steam distillation, an oil of camphoraceous odour passed over. A small quantity of a second crystalline, but not basic,compound, not yet investigated, was produced in both cases, and was extracted from the alkaline residue. Pinene nitrosocyanide dissolves in concentrated sulphuric acid with- out coloration but with evolution of considerable heat, The solution, when diluted with water, yields the unchanged nitrosocyanide, but when the solution in sulphuric acid is digested at about 100' for an hour or two, the addition of water does not cause an immediate precip- itate.On allowing the liquid to stand, a new compound is deposited in tufts of crystals, which, after recrystallisation from alcohol, appear in the form of well-defined plates which melt and decompose at about 220'. It is soluble in aqueous potash, and, somewhat strangely, also in hydrochloric acid. This compound contains 14.38 per cent. of nitrogen, which corresponds closely with the amount required either by a polymerised product, (C,oHl,mNO-CN),, or by the product which would result from the formation of the corresponding acid amide and the subsequent elimination of water, thus : N io This is, however, a subject for further investigation. Pinene nitrosocyanide, placed in contact with warm nitric acid (sp.gr. 1*4), liquefies but does Dot dissolve, while a small quantity of nitrous gas is evolved. In a few minutes, the reaction seems to be complete, effervescence ceases, and on pouring the whole into cold water, a solid is precipitated which crystallises readily from alcohol in colourless prisms. This compound is insoluble iu aqueous alkali. It melts with decomposition at 105'. Analysis gave 16.30 per cent. of nitrogen. The formula of a mononitrocyanide, C,,H1,*NO,*CN, requires 13.46, while that of a dinitrocyanide, C,,H,,(NO,),CN, requires 16.60 per cent. of nitrogen. It is probable, therefore, that the nitroso-group is oxidised and nitration occurs at the same time. An attempt to produce a nitrosocyanide from limonene nitroso- chloride gave a liquid product which is awaiting further investiga- tion.Terpinene nitrosate is also expected to yield corresponding products. With regard to the hydrochlorides obtainable from pinene, the monohydrochloride (m. p. 128') refused to react under any circum- stances with either cyanide of potassium or of silver, An alco- holic solution of dipentene dihydrochloride digested with potassium 164 cyanide in the cold for 14 days gave the liquid monohydrochloride, CloH16,HCl, and the latter, by continuing the action of the cyanide at about 120°, gave very pure terpinene, which was identified by its boiling point (181O) and by the production of the characteristic crystalline nitrosate. "108.''The colour changes exhibited by the chlorides of cobalt and some other metals from the standpoint of the theory of electro-affinity." By F. G. Donnan and H. Bassett, jun. The colour changes exhibited by aqueous and alcoholic solutions of the chlorides of cobalt, copper, and ferric iron on variation of tempera- ture or dilution, or on the addition of various chlorides, such as those of hydrogen, calcium, magnesium, zinc, mercury, are shown to be largely due to the formation or dissociation of complex anions contain- ing a metallic atom in association with chlorine. Evidence was brought forward to show that the dehydration theory is inadequate to explain the observed phenomena. Experiments on the motion of boundaries between different liquid layers on the passage of an electric current point to the existence of complex negative ions.Thus, in the case of cobalt chloride, the blue solutions travel towards the anode, the red solutions towards the cathode. Further experiments on the combination be- tween cobalt and other chlorides in aqueous and alcoholic solutions admit of explanation on the above hypothesis. "109. ''The stereochemical formulae of benzene." By J. E. Marsh. The author discussed the objections to the stereocentric formulae of benzene brought forward by Graebe (Ber., 1902, 35,526), and pointed out that according to the latter, rings identical in structure, which their properties do not admit of, would be assigned to benzene and naphtha- lene. The author considers that all the eight stereocentric formula are possible for benzene and its derivatives ; that orthophthalic acid would have the trans-centric form, in which case it could form an anhydride, though the meta-acid could not, since the hexahydro-ortho- acid alone forms an anhydride in the trans-form.Thus, proximity of groups alone would not account for the formation of anhydrides, nor of carbonates and methylene ethers of dihydric phenols. Further, the absence of optically active compounds is accounted for if we regard the Kekul6 formula as a labile form of the cis-centric, for the Kekul6 model can close in in two ways to form cis-centric formulae, one being the optical image of the other. With regard to substitution, those compounds which yield meta-derivatives contain an oxidisable group, whilst those which yield ortho- 165 and para-derivatives contain a reducible group.In the former case, the repulsion of hydrogen leads to the trtcm-centric form with produc-tion of meta-derivatives. In tvhe latter case, the attraction of hydro-gen to the group leads to cis-centric hydrogen in the ortho- and para- positions. Bamberger’s dicen tric formula for naphthalene was also criticised, as it appears stereochemically impossible and is not in accord with the constitution of allied hydrocarbons. *110.(L An accurate method of determining the compressibility of vapours.” By B. D. Steele, D.Sc. In the course of an investigation with Prof. Ramsay, it became necessary to determine, with a high degree of accuracy, the compres- sibility of certain vapours at low pressures.The apparatus employed consists of a combination of volume apparatus and pressure gauge, so constructed as to be capable of being contained together in a glass jacket which can be maintained at a constant temperature. The pressure is measured by setting two surfaces of mercury to carefully ground glass points the difference in level between which is known. The volume is obtained by weighing the mercury entering or leaving the apparatus. Experiments with the vapours of benzene and ether have been made in the apparatus, and curves obtained showing the variation of PT with P for pressures varying from 40 to 200 mm. *111. &‘Anew type of substituted nitrogen chlorides.” By F.D. Chattaway. No substituted nitrogen chlorides known up to the present have three negative groups attached to the nitrogen. All contain at least one hydrocarbon residue. Such a series of compounds of the type z>N*CI, where R and R are acyl groups, is yielded by the diacyl amides. These, when treated with hypochlorous acid or, under certain conditions, with chlorine have their imino-hydrogen replaced by chlorine, thus : The diacyl nitrogen chlorides are colourless, well-crystallised com-pounds which show the typical behaviour of substances having halogen attached to nitrogen. Dibenzoyl Nitpogen ChZ oride, ;:2::>N*Cl.-In order to obtain 166 this compound, dibenzamide, prepared by the action of fuming sul- phuric acid and phosphorus pentoxide on benzonitrile, was dissolved in acetic acid.To the solution, an excess of a strong solution of bleaching powder was added. Chlorine was vigorously evolved and a yellow oil separated. Chloroform was added and the whole well shaken for a few minutes. The chloroform solution was then run off, washed with water, and finally with a dilute solution of potassium bicarbonate, dried over fused calcium chloride, and the solvent evaporated at a low temperature in a rapid current of dry air. The nitrogen chloride crystallised out as a white solid (m. p. 89’), readily soluble in chloro-form and in benzene, but sparingly in petroleum. It crystallises from a mixture of chloroform and petroleum (b. p. 60-80°) in colourless, six-sided prisms with domed ends.It was analysed in the usual way, by adding an excess of hydriodic acid to a weighed quantity dissolved in chloroform, and estimating the liberated iodine by a standard solu- tion of sodium thiosulphate : 0.2446 liberated I =18.7 C.C. X/lO I. C1 as :N*CL= 13-55, C,,Hlo02:N*Clrequires C1 as :N*Cl= 13.65per cent. When heated with water or dilute acids it is hydrolysed, hypochlor- ous acid being liberated and dibenzamide re-formed, the latter under- going further hydrolysis to benzoic acid and benzamide, and finally, if the heating be prolonged, to benzoic acid and ammonia. CH *C”H *CO C1. -Th is was pre- Di-p-toZuy I Nitrogen Chloride, CHS. ZH4. co>N ’ 364 pared from di-ptoluylamide by the method previously described.It closely resembles the dibenzoyl derivative in properties and in solubility. It crystallises in long, colourless, six-sided prisms with domed ends (m. p. 129’). 0-2121 liberated I = 14.8 C.C. N/10 I. C1 as :N*Cl= 12.37. C,6Hl,02:N*C1 requires Cl as :N*Cl= 12.32 per cent. The author desires to reserve the further investigation of these and similar compounds. *112. “The preparation of pure chlorine and its behaviour towards hydrogen.” By J. W. Mellor and E. J. Russell. A quantity of carefully dried and purified silver chloride was placed in a V-shaped tube of the hardest Jena glass, in which were also in-serted, as electrodes, stout carbon rods specially prepared for the electrolysis of fused salts. An air-tight joint having been made, the salt was fused and a current of 2.8 amperes passed through.Chlorine was evolved in a steady stream. Foreign gases and mois- 167 ture were removed by occasional reversal of the current and re-peated exhaustion with an automatic Sprengel pump. The silver tree was destroyed by raising the temperature and increasing the current to 5 amperes. The tree then either melted or was shattered ; electrolysis was discontinued until the former temperature was restored; when started again, it was found to pro- ceed in a normal manner. Hydrogen was prepared by the action of steam on sodium and was absorbed by palladium. The whole apparatus was then exhausted, the palladium heated, and hydrogen evolved. The gases were sealed up in the inner and outer bulbs respectively of the condensers now largely used with Soxhlet extractors.Each bulb contained a quantity of carefully purified phosphorus pentoxide, the inner bulb containing also a small piece of glass rod. After drying for some months in the dark, the vessels were shaken to break the inner bulb and the gases mixed by diffiision. Only condensers which had approximately equal capacities for the inner and outer bulbs were used ; hydrogen was put in at the same pressure as the chlorine, so that the volumes of the two gases were nearly equal. A small electric spark passed through a mixture sor obtained caused an explosion, and combination was found to have been practically complete. Apparently drying does not affect the action of the spark.Mixtures of moist hydrogen and chlorine in similar bulbs were found to explode at about 260O. One of the bulbs containing the purified mixture was therefore heated to 2’70’ for some minutes, but no explosion took place. On opening the bulb, it was found that there had been practically no combination. Another bulb was heated for 10 minutes to 450’. Still no explosion occurred, but about 80 per cent. of the mixture had combined. Some of the phosphorus pent- oxide had volatilised, and as it was found impossible to heat the gases without also heating the pentoxide, ib is still uncertain whether this slow combination is a direct action or a surface action. Another bulb was exposed to bright sunshine at Wye for 3 days, but no explosion took place; and only about 30 per cent.of the hydrogen and chlorine had combined. *113. ‘‘ Derivatives of dibenzoylmeaitylene.” By W. R.Mills and T. H. Easterfield. The authors described a method of preparing dibenzoylmesitylene by which it may be obtained in quantity, and methods for the production and isolation of the five acids which result by the successive oxidation of its methyl groups, namely, asymdibenzoylmesitylenic acid, m. p. 1744 sym.dibenzoy1mesitylenic acid, m. p. 222O, asym.dibenzoyluvitic 168 acid, m. p. allo, sym.dibenzoyluvitic acid, m. p. 362O, and dibenzoyl- trimesic acid, m.p. 2509 A mixture of these, of which asynz.dibenzoylmesitylenic acid is by far the largest constituent, is obtained by boiling the ketone with dilute nitric acid the boiling point of which has been raised by the addition of large quantities of potassium and sodium nitrates. The two dibenzoyluvitic acids are most conveniently prepared by treating the easily obtainable asym.dibenzoylmesity1enic acid with one equivalent of potassium permanganate in alkaline solution.If double this amount of potassium permanganate be used, dibenzoyltrimesic acid is obtained. The constitution of these acids readily follows from the following facts : Me CO,H sz&z Me1\/}Me I. 11. Me CO,H UO,H The dibenzoylmesitylenic acid of melting point 174O, oxidised with potassium permanganate, yields a mixture of both dibenzoyluvitic acids. It must therefore be the asymmetrical acid of formula I.The dibenzoylmesitylenic acid of melting point 222O, similarly treated, yields only one dibenzoyluvitic acid meIting at 211'. Hence, it must be represented by formula I1 and the dibenzoyluvitic acid resulting from it by IV. The dibenzoyluvitic acid melting at 262' must there- fore be represented by 111, and for dibenzoyltrimesic acid, only one formula is possible, namely, V. In working with these acids, the fact was discovered (also noticed by Graebe, Ber., 1900, 33,2026) that diortho-substituted acids do not obey V. Meyer's esterification rule when the ortho-substituents are benzoyl groups : CO,H x/\,xCH,!,/CH, HO,C()CH, VI. VII. whereas it follows from V. Meyer's work that the esterification con-stant of an acid of formula VI would in general be indefinitely smaller at the ordinary temperature than that of an acid of formula VII, in 169 the case where X is a benzoyl group it is smaller only in the ratio of approximately 0.65 to 1.0.114. “The molecular condition of borax in solution.” By H. S. Shelton. Borax (Shields, Phil. M(cg., 1893,135,365)is slightly hydrolysed into sodium hydroxide and boracic acid, Experiments on the diminution of conductivity on the addition of further quantities of boracic acid show an increase of this hydrolysis when further diluted with water, and also with increase of temperature. In N/10solution, the hydrolysis was estimated by Shields to be 0.5 per cent, at 25’, and the experi- ments of the author with N/200 solution showed 4 per cent.at 25’ and 6 per cent. at 50’. Kahlenberg and Schreiner (Zeit.Phys. Chenz., 1896, 20, 547) concluded from freezing point determinations that six ohemical individuals are present in a dilute solution of borax. These chemical individuals seem to be 2H3B0,,5?NaB0,, as shown by f-the following equation : Na,B,O,Aq +3H,O =2NaAq,2B02Aq +2H,BO,. The author has confirmed this by a number of direct experiments, amongst which the most important is the precipitation of AgBO,, and determination of the boracic acid remaining in the solution. 115. “On the union of hydrogen and chlorine. Part V.” By J. W. Mellor, D.Sc. There is no experimental evidence to show that chlorine gas under the influence of light undergoes any change capable of appreciably affecting the chemical activity of that element towards hydrogen.Part of the energy absorbed by moist chlorine from sunlight is dissipated as heat. This causes the Budde effect. Under the influence of light, chlorine sets up and maintains in a state of equilibrium a reversible reaction with water vapour, possibly 2H,O +2C12=4ElX1 +0,. Dry chlorine does not exhibit the Budde effect. The rise in temperature of imperfectly dried chlorine when exposed to sunlight appears to be due to some chemical reaction between the moisture and the chlorine gas. A layer of moist chlorine just thick enough to screen a bulb of mixed hydrogen and chlorine gases from chemical action is not sufficient to prevent chemical action if the chlorine is dried by means of purified phosphorus pentoxide.The actinic energy con-tinuously absorbed from sunlight by moist chlorine is dissipated in at least three ways :(1) in maintaining the above chemical reaction 170 (2) by conversion into heat during molecular impacts; (3) as ex-ternal non-actinic radiations from t,he molecules moving in their free path between molecular collisions. 116. ‘‘ On the union of hydrogen and chlorine. Part VI.” By J. W. Mellor, D.Sc. If the reaction between hydrogen and chlorine in the presence of moisture is assumed to take place with the formation of an inter-mediate compound, the period of induction is a direct consequence of the law of mass action. Since neither chlorine monoxide nor hydrogen hypochlorite abbreviate the period of induction, neither of these substances can take part as intermediate compounds in the reaction between hydrogen and chlorine.Since chlorine acquires no appreci- able chemical activity by exposure to sunlight, the presence of hydro-gen as well as of moisture determines the greater chemical activity of an induced mixture of hydrogen and chlorine gases. If an intermediate compound takes part in the reaction between hydrogen and chlorine in the presence of moisture, the most probable “compound ” satisfying the required conditions contains xCll,,yH,O,xH,, where x, y, z, are positive integers. The explanation ofiered by the two dependent re- actions involved in the equation, remains to be studied.117. “On some hydroxy-pyrone derivatives.” By T. Tickle and J. N,Collie, F.R.S. During some work on the constitution of meconic acid, the authors found that it was necessary to prepare certain hydroxypyrone deriv- atives in order to compare their properties (especially their colour reactions with ferric chloride) with those of meconic acid. Dirnethylpyrone, when treated with hydrogen peroxide in presence of a ferrous salt, yields hydroxydimethylpyrone, C7H,02+ H202= C7H,0, + H20. This substance crystallises from water in colourless needles ; it can be sublimed without decomposition and melts at 162P. With ferric chloride, it gives a deep violet-blue colour. Its monacetyl derivative melts at 98O and does not colour an aqueous solution of ferric chloride.Meconic acid, when treated in the same manner with hydrogen peroxide, gives carbon dioxide and hydroxycomenic acid, C7H,07+ H,O, =C6H,0, + CO, + H20. Hydroxycomenic acid seems to be a dibasic acid; it gives an intense violet with ferric chloride, melts at 171 275O, and crystallises from water in long, fine needles. It seems probable that this is the same acid as that first obtained by Reibstein (J.p.Chsm., 1881, [ii], 24, 286) by the action of barium hydroxide on bromocomenic acid. He, however, gives no melting point for the acid, but only for the ethyl ester, 204O, and for the diacetoxyl derivative, 76". The authors find that these derivatives prepared from this acid melt at 207.5O and 75' respectively, All attempts to prepare either meconic acid or hydroxycomenic acid by oxidation of chelidonic acid were unsuccessful.118. "The absorption spectra of phloroglucinol and some of its derivatives." By W. N. Hartley, D.Sc., F.R.S.,J. J. Dobbie, D.Sc., M.A., and A. Lauder, B.Sc. Phloroglucinol reacts with some reagents as a phenol, with others as a ketone. It is impossible, therefore, from its chemical behaviour to decide whether its oxygen atoms are present in hydroxyl groups or in direct union with carbon. The trimethyl derivative of phloroglucinol (m. p. 52') is regarded as a true ester, since its methoxyl groups are split off by heating with hydrogen iodide. The absorption spectra of this substance and of phloroglucinol were found to be almost identical.From this it follows that if the structure of the ester has been correctly established, phloroglucinol also must have the enolic structure (Tmns., 1899, 76, 640; 1900, 77, 839). Aqueous and alcoholic solutions of phlorogliicinol show both general and selective absorption. A layer 50 mm. thick of a solution containing 1milligram-mol. in 20 C.C. water, absorbs all rays beyond X 3009, whilst a layer 5 mm. thick absorbs all rays beyond h 2802. The absorption-band is not strongly marked; it appears first in a layer 3 mm. thick of the solution containing 1milli-gram-mol. in 100 C.C. water, and nearly dies out in a layer 2 mm. thick, although its position is still distinctly traceable by the weakness of the spectra in solutions of greater dilution. The resemblance be- tween the spectra of phloroglucinol and the trimethyl derivative is so close that phloroglucinol cannot consist of a mixture of the enolic and ketonic forms.The specimens of phloroglucinol examined were prepared from five different sources, namely, kino, maclurin, resorcinol, phenol (by fusion with sodium hydroxide), and phloroglucinoltricarboxylic ester. The specimens from these various sources had the same melting point. The melting point is greatly influenced by the rate of hsating, varying between 210° and 217O. The absorption curves of all the specimens agree perfectly. The authors conclude from the identity of the spectra that the structure of phloroglucinol, no matter from what source it is obtained or by what method it is prepared, is always the same.172 The spect,ra of pyrogallol were also re-examined, and the curve was foiind to resemble very closely that of phloroglucinol, thus confirming the conclusion that the latter substance has the enolic structure. 119. (( Solubility of mannitol, picric acid, and anthracene.” By A. Findlay. Determinations of the solubility of rnannitol in water, of picric acid in water and in benzene, and of anthracene in benzene, have been made at several temperatures between 25” and 60’. It has already been shown by the author (P~oc.Roy. Xoc., 1902, 69, 471) that if the solubility curve of one substance is known, that of another substance can be calculated from two, or better, three, determinations of the solubility of the second substance at different temperatures.The formula used for this purpose is one analogous to that employed by Ramsay and Young for the calculation of vapour pressures, and has the form 5!’JTl’= T2/Ti+c(t’ -t), where Tl/Fl‘ and T2/Z’idenote the absolute temperatures at which the two substances have the same solubility, c is a constant, and t’ and t are the tempera- tures at which one of the substances has the solubility corresponding to the absolute temperatures Tland Fzor T1’and Ti. This formula has been employed in the present case for calculating the solubilities and 25O, and between 60’ and looo (in the case of anthracene and picric acid, in benzene up to the boiling point of the latter).120. Menthyl formylphenylacetate.” By J. B. Cohen and S. H. G. Briggs. A short time ago, the aathors commenced a similar investigation to that of Lapworth and Hann (this vol., p. 144) with the object of study-ing tautomeric changes by means of optically active substances, in the course of which they prepared menthyl formylphenylacetate described by Lapworth and Hann. As the authors do not intend, under the circumstances, to pursue this line of inquiry, they desire to record their observations, which, though they confirm on the whole the re- sults given in the paper referred to, show some slight differences. Menthyl formylphenylacetate was prepared as follows. Sodium was allowed to act on a mixture of menthyl acetate and ethyl formate dis- solved in dry ether.In this reaction, an interchange occurs to some extent between the menthyl and ethyl groups so that some menthyl formate, and some ethyl formylphenylacetate are produced. The pro- duct was poured into water, the ethereal layer removed, and the aqueous portion acidified and shaken out with ether. The ether was 0’ of the above substances between 173 evaporated in a vacuum, and crystals of menthgl formylphenylacetate separated on standing. The menthyl ester thus obtained was in the form of large, well-formed, tetragonal crystals consisting of four-sided prisms terminated by pyramids ; purified by recrystallisation from chloroform, it melted at 82-84' (L. and H. give 82-83'). The specific rotation of a freshly prepared chloroform solution contain- ing about 3 grams of substance in 100 C.C.is [cc]~= -72.6' (L. and H. give -74.6'). In an alcoholic solution containing 2 grams in lOOc.c., the specific rotation was [a]F= -63.4' (L. and H. give -64.9'). The addition of sodium ethylate did not affect the rotation. The following were the effects of an alcoholic solution of ferric chloride on the substance when dissolved in various solvents. A faint violet coloration wa8 produced in methyl and ethyl alcohol, ether, and light petroleum. No coloration was produced at first in benzene, chloroform, or ethyl acetate but slowly developed. Menthyl phenylacetate, ob- tained iu the preparation of the forrnylphenylacetate, is a colourless and odourless liquid which boils at 216' (39 mm.)."121. Transformation of diacetanilide into aceto-pamino-aceto- phenone." By F. D. Chattaway. A large number of derivatives of primary aromatic aminos in which various atoms or groups are attached to the nitrogen readily undergo intramolecular transformation and form isomerides in which the atom or group is attached to the nucleus in the para- or ortho-position. The best known examples of such changes are those in which a halogen atom, a nitro-group, a sulphonic group, or a hydroxyl group passes on to the ring. So far, however, the commonest substi- tuting group in amines, the acetyl group, has not been observed to wander. The author described experiments in which this group passed into the ring in the normal manner.The substance studied was diacetanilide, which underwent transformation into aceto-p-amino-acetophenone. 122. '(Nitrogen chlorides and bromides derived from ortho-substi- tuted anilides." By F. D. Chattaway and J. M.Wadmore. Nitrogen halogen derivatives of orthochlorobenzanilide and ortho- bromobenzanilide, which have not hitherto been described, are easily obtained by treating the corresponding anilides with an excess of hypochlorous or hypobromous acid, the actions, as in other similar cases, being reversible. The nitrogen chlorides and bromides so ob-tained show all the typical nitrogen halogen group reactions and readily undergo transformation into the isomeric 2 :4-disubstituted a nili de s. 174 The following compounds have been prepared : BenzoyI-o-chloropheny1 nitrogen chloride, C,H, C 1 NC1 COc16H5,c ol our -less, six-sided plates, m.p. 94". Benxoyl-o-ehlorophenyl nitrogen bromide, C6H4Cl*NBr*COCGH5,short prisms of a deep yellow colour, m. p. 110'. o-Bromobenxunilide, C6H4Br*NH*COC6H,, colourless, rectangular plates, m. p. 116'. Benxoyl-o-bromophengl nitrogen chloride, C,H4Br*NC1-COC6H5, colourless, transparent prisms, m. p. 85O. Benzxoyl-o-bomophenyl nitrogen bromide, C6H4Br*NBr*COC6H5,yellow, six-sided, rhombic prisms, m. p. 9 9'. Acetyl-o-chlorophenyl nitrogen bornide, C,H,CI*NBr*COCH,, pale yellow, four-sided prisms, m. p. 152'. Acetyl-o-bromophenpl nitrogen chloride, C,H,Br*NCl-COCH,, colourless, four-sided prisms, m. p. S6O. 123. c4 Substituted nitrogen chlorides containing the azo-group." By F.D. Chattaway. In order to determine the effect of an azo-group on the properties and direction of transformation of nitrogen chlorides, a number of such compounds have been prepared from aminoazobenzene. Amino-azobenzene yields well crystallised acetyl, propionyl, and benzoyl derivatives, which react with hypoclilorous acid very readily and form nitrogen chlorides possessing all the characteristic properties of the nitrogen halogen group. This adds another to the many reasons for regarding aminoazo-compounds as primary amino-derivatives. The following compounds have been prepared : p-Acet?/lchZoroaminoaxobenxene,C,H,*N:N*C6H,*NC1* COCH,, orange- red plates, m. p. 113.5'. Pwpion y 1-p-aminoaxobenxene, C,H5*N:N*C6H;NH*COC,H,, large, orange-red plates, m.p. 170'. p-Propionylchlorouminoazobenzene, CsH50N:N*C6H,*NC1.COC,H5, red prisms, m. p. 57'. Benxoyl-p-ccnt,inoazo benzene, C,H,*N:N=C,H;NR*COC,H,, reddish-orange plates, m. p. 21 1'. p-~enxoy&?o!rouminoazo6enxene, CGH5'~:NoCAH4=NCl*COC6H~,red-brown, glistening, flattened prisms, m. p. 144'. 124. (6 The action of chlorine and bromine on nitroaminobenzenes. Part I. 8-Trisubstitutedchloronitroaminobenzenes."By K.J. P.Orton. In the course of an i1,ivestigation of the conditions under which the nitroamines derived from s-trisubstituted anilines (this vol., p. 111) are transforiiied into substances containing the nitro-group in the benzene nucleus, the action of chlorine and bromine on these substances was studied.When chlorine is passed into an aqueous solution of the sodium salt of a nitroamine, or when dilute aqueous bleaching powder is slowly added to a solution of the nitroamine in acetic acid, the chloronitro- 175 amine is formed ;thus 1-nitroamino-s-trichlorobenzeneyields 1-chloro-nit~oamino-~-trichlroben2ene,C6H,Cl,*NC1*N0,. As the sodium (and other) salts of the nitroamines may probably be represented by the formula R*N:NO*ONa, and, if so, would be the salts of a substituted ''iminonitronic acid " (compare Bamberger, Ber., 1902, 35, 54), the author suggested that the reaction of chlorine with the sodium salt might be represented thus : + + R*N:NO*O+Na + C1, -+ R*y*qO*O+ Na --+ c1 c1 -+ R*NCl*NO,+ C1+ Na.All these chloronitroamines are very unstable, and are reconverted by all reagents into the nitroamines. The following compounds, all of which crystallise in lustrous, colourless prisms, have been prepared : 1-ChZoronitroamino-s-trichZorobenxene,m. p. 53-54' ; 1-chloronitro-amino-s-tribromobenxene, rn. p. 6 1' ; 1-chloronilYoanzino-4-chZoro-2 :6-di-bromobenzene, m. p. 56" ; 1-clzloi~onitroamino-2: 3 : 4 : 6-tet~ccbromo-benzene, m. p. 61-62' ; 2-chloronitroamin~-3: 5-clib~omotoZuene,m. p. 60' ; 4-chloronit~oamino-3:5-dibromotoEuene,m. p. 50-51'. By the action of bromine on aqueous solutions of the sodium salts of the nitroamines, the bromonitroamino-derivatives are form ed, but have not been obtained free from the nitroamine.125. The transformation of diazoamido- into aminoazo-compounds and of hydrazobenzene into benzidine." By F. D. Chattaway. The transformation of diazoamido- into the isomeric aminoazo-deriv- atives is similar in nature to the other well-known transformations in which atoms or groups of atoms pass from the ni+rogen of an amino- group attached to a benzene nucleus into the para- or ortho-position in the ring, thus : As is usual in these intramolecular changes, the para-position is taken up by preference, the ortho-position to a less extent, or exclu-sively when the para-position is already occupied. This analogy is somewhat obscured by the ordinary method of representing the transformations, 176 where the NH group appears to leave the chain and pass into the ring.The formation of the various azo-derivatives which are obtained by heating diazoamido-compounds with aromatic amines and their hydro- chlorides, is thus rendered intelligible without assuming the formation of intermediate Eitrogen halogen compounds (Goldschmidt and Bardsch, Ber., 1892, 25,1376). It is only necessary to assume the existence of a mobile hydrogen atom and double linkage in the diazoamido-compounds, and to admit that the diazo-group can undergo transference from the nitrogen atom of one amine to that of another, present in large excess, exactly as a chlorine or bromine atom does. Much that is known of similar isomeric changes points to the conclusion that transference from nitrogen to the ring can only take place when the nitrogen is exerting its higher valency.This may explain the advantage, in these transformations, of the hydrochloride of the base. The isomeric change of hydrazobenzene into benzidene is also brought into line with other analogous transformations if similarly formulated : NH2 I It is seen to consist of two stages, of which the first only can take place if the para-position is already occupied, the semidine and other similar transformations resulting : I/'\ I -+ /)-NH*c,H,. \/ \jCOCH, COCH, As is well known, the related ortho-change also takes place to some extent with the formation of diphenyline, in all probability, the ortho-change also takes place to a relatively very small extent in the second stage with the production of diorthoamino-diphenyl, though the latter is produced in such small quantity that it has hitherto escaped detection.126. LL Tribromophenolbromide.” By E.W.Lewis. A re-examination of this substance has shown that the melting point usually attributed to it (118’) is much too low, and that it may be raised to 148-149’ by recrystallising the compound from ethyl acetate; moreover, whilst, as usually stated, the substance of low melting point gives off bromine on heating at about l25’, the purified material begins to lose bromine before melting at about 145O. The crystals of tribromophenolbromide belong to the orthorhombic system, the axial ratios being cc : b :c =0.7945 :1 :1.5921.ADDITIONS TO THE LIBRARY. I. Donations. Mann, Harold H. Studies in the chemistry and physiology of the tea leaf. Part I. The enzymes of the tea leaf. Pp. 13. 1901. From the Author. Prescott, Albert B., and Eugene C. Sullivan. First book of qualitative chemistry for studies of water solution and mass action. 11th ed. Pp. 148. New York 1902. From the Publishers. Taylor, R. L. The student’s chemistry ;being outlines of inorganic chemistry and chemical philosophy. 3rd ed. Pp. 343. London 1901. From the Author. Catalogue of scientific papers (1800-1883) supplementary volume. Compiled by the Royal Society of London. Vol. xii. Pp. S07. London 1902. From the Royal Society. Fowler, Gilbert J. Sewage works analyses. Pp. 135. London 1902. From the Publisher.Sorel, E. La grande industrie chimique minhrale. Soufre. Azote. Phosphates, Alun. Pp. 809. Paris 1902. From the Publishers. 11. By Purchase. Duhem, E. Le mixte et la combinaison chimique, essai sur l’evolu- tion d‘une idhe. Pp. 207. Paris 1902. Kohlrausch and Holborn. Das Leitvermogen der Elek trolyte insbesondere der Losungen. Methoden, Resultate, und chemische Anwerdungen. Pp. 21 1. Leipzig 1898. Pettenkofer, Max v. Uber Olfarbe und Conservirung der Gemalde- Galerien durch das Regenerations-Verfahren. Zweite Auf. Pp.183. Braunschweig 1902. Fischer, Ferdinand. Das Wasser, seine Verwendung, Reinigung, und Benrtheilung mit besonderer Beriicksichtigung der gewerblichen Abwiisser und der Flussverunreinigung. Dritte umgearbeitete Auf.Pp. 482. Berlin 1902. Dehdrain, P. P. Trait4 de chimie agricole. DQveloppement des vdgktaux, terre arable, amendements, et engrais. Deuxibme Bd. revue et augmentde. Pp. 969. Paris 1902. Vogel, Otto. Jahrbuch fur das Eisenhuttenmesen. (Erganzung zu ‘‘ Stahl und Eisen.”) Ein Rerichte uber die Fortschritte auf allen Gebieten des Eisenhuttenwesens im Jahre 1900. I. Jahrgang. Pp. 459. Dusseldorf 1902. Wilfarth, H., and G. Dimmer. Die Wirkung des KaIiums auf das Pflanzenleben nach Vegetationsversuchen rnit Kartoff eln, Tabak, Buchweizen, Senf, Zichorien und Hafer. (Arbeiten der Deutschen Landmirtschafts-Gesellschaft. Heft. 68.) Pp. 106. Berlin. Schmucken, BIartin. Secretorum Naturalium, Chymicorum, et Medi- corum Thesauriolus, oder Schatzkiistlein darinnen 20 naturliche, 20 chymische, und 20 medicinische Secreta, und Kunst Stucklein zu befinden, durch vielfaltige Reisen, Muhe, und Gefahr colligiret, und an Tag gegeben, von M.S, Lipsensi, der Artzeney Licenciato. Pp. 80. Schleusingen 1637. Thesaurioli. Pars altera. Pp. 104. Nurnberg 1637. Kesler, Thomas, Keslerus redivivus das ist F’linff Hundert ausser- lesene chymische Process und Artzneyen, theils zu innerlichen und eusserlichen Leibskranckhaiten theils auch zu Verbesserung der mindern Metallen hochnutzlich. Deren erstlich Vier Hundert durch T. K. Chymicum et civem Argentinensem an Tag gegeben und zum vierdten ma1 auffgelegt, an jetzo aber von einem vornehmen Chymico auffs new ubersehen, und mit Hinzusetzung dess fiinfften- hunderten in formliche Ordnung und gewisse Classes gesetzet. Yp. xvi + 550. Frankfurt-a,-M. 1641. LIBRARY. The Library mill be closed for stock-taking during the first fortnight of August. Fellows are particularly requested to return all Library books in their possession not later than July 26th. RICHARD aLAY AKD SONS, IIPIIITED, LONDON AND BUNGAY
ISSN:0369-8718
DOI:10.1039/PL9021800159
出版商:RSC
年代:1902
数据来源: RSC
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